CN113451629B - Low-cost ferrotitanium flow battery - Google Patents

Low-cost ferrotitanium flow battery Download PDF

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CN113451629B
CN113451629B CN202110795255.1A CN202110795255A CN113451629B CN 113451629 B CN113451629 B CN 113451629B CN 202110795255 A CN202110795255 A CN 202110795255A CN 113451629 B CN113451629 B CN 113451629B
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CN113451629A (en
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马相坤
乔琳
房茂霖
南明君
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Dalian Maritime University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to the technical field of flow batteries, in particular to a low-cost iron-titanium flow battery. The battery consists of a battery module, an anode electrolyte liquid storage tank and a cathode electrolyte liquid storage tankThe battery module is formed by connecting one or more than two single cells in series, each single cell comprises an electrode end plate, a bipolar plate, an electrode, an ion conducting membrane and an electrode frame, an anode electrolyte liquid storage tank is communicated with the anode of the battery module through an anode circulation pipeline, and a cathode electrolyte liquid storage tank is communicated with the cathode of the battery module through a cathode circulation pipeline; the negative electrode redox couple of the battery is Ti 3+ /Ti 4+ The positive electrode redox couple is Fe 2+ /Fe 3+ The supporting electrolyte is an inorganic acid or an organic acid. The ferrotitanium flow battery has the characteristics of long cycle life, environmental friendliness, simple structure and simple manufacturing process.

Description

Low-cost ferrotitanium flow battery
Technical Field
The invention relates to the technical field of flow batteries, in particular to a low-cost iron-titanium flow battery.
Background
With the development of economy, the demand for energy is increasing, and environmental problems caused by the massive consumption of fossil energy are increasingly highlighted. The large-scale utilization of renewable energy sources and the realization of energy diversification become important strategies for the safety and sustainable development of energy sources of countries around the world. However, the discontinuity and instability of renewable energy sources such as wind energy and solar energy make their direct use difficult, so that the realization of continuous supply of renewable energy sources by using energy storage technology becomes a key to solve the above problems. The flow battery has the advantages of flexible design (capacity and power are separately designed), good safety and long service life, and becomes one of the technologies with the optimal prospect of large-scale energy storage market.
The flow battery system which is developed at present comprises all-vanadium flow battery, zinc-bromine flow battery, sodium polysulfide bromine and other systems. However, the all-vanadium redox flow battery has the problems of higher cost and stronger acidity and corrosiveness of electrolyte; in addition, zinc-bromine flow battery systems and sodium polysulfide-bromine systems face the problems of bromine volatility and corrosiveness, and the environmental pollution is serious. It is therefore important to develop new flow batteries that are low cost, environmentally friendly, and highly reliable.
Disclosure of Invention
Based on the technical problems, the invention provides a low-cost ferrotitanium flow battery which has the characteristics of long cycle life, environmental friendliness, simple structure and simple manufacturing process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the utility model provides a ferrotitanium flow battery, the battery comprises battery module, positive pole electrolyte liquid storage pot, negative pole electrolyte liquid storage pot, circulating pump I, circulating pump II, circulation pipeline, the battery module is established ties by one or more single cell and is formed, the single cell contains electrode end plate, bipolar plate, electrode, ion conducting membrane, electrode frame, positive pole electrolyte liquid storage pot communicates with each other with the positive pole of battery module through positive pole circulation pipeline, negative pole electrolyte liquid storage pot communicates with each other with the negative pole of battery module through negative pole circulation pipeline, the negative pole redox couple of battery is Ti 3+ /Ti 4+ The positive electrode redox couple is Fe 2+ /Fe 3+ The supporting electrolyte is an inorganic acid or an organic acid, and comprises one or a mixture of more of sulfuric acid, phosphoric acid, chloric acid, hydrochloric acid and methane sulfonic acid.
Further, during charging, the positive electrolyte and the negative electrolyte are respectively conveyed to the positive electrode and the negative electrode from the positive electrolyte liquid storage tank and the negative electrolyte liquid storage tank respectively through the circulating pump I and the circulating pump II, ti 4+ Reduction of ions to Ti at the negative electrode 3+ Ion, fe 2+ Oxidation of ions to Fe at the positive electrode 3+ The method comprises the steps of carrying out a first treatment on the surface of the Upon discharge, ti 3+ Oxidation of ions to Ti at the negative electrode 4+ The ions return to the negative electrolyte storage tank through the circulating pump II; fe (Fe) 3+ The ions are reduced to Fe at the positive electrode 2+ Ions are returned to the positive electrolyte reservoir via the circulation pump i.
Further, the positive and negative electrolyte is an acid solution containing iron ions and titanium ions, and the concentration of the iron ions is 0.1-5 mol & dm -3 The concentration of titanium ions is 0.1 to 5mol dm -3 The concentration of the acid is 0.1 to the whole6mol·dm -3 。
Further, the working temperature of the battery is-20-80 ℃.
Further, the positive electrode and the negative electrode of the battery are made of metal or carbon materials with plate-shaped structures or porous structures, and the carbon materials comprise carbon cloth, carbon paper and carbon felt.
Further, the ion conducting membrane is an ion exchange membrane or a porous membrane.
Compared with the prior art, the invention has the following advantages:
the invention provides a low-cost and high-performance iron-titanium flow battery, which adopts acid solutions such as sulfuric acid, phosphoric acid and the like as supporting electrolytes to avoid precipitation of negative electrolyte; the positive and negative electrolyte is the same, so that cross contamination of the positive and negative electrolyte can be avoided, the cost of the flow battery can be greatly reduced by selecting iron ions and titanium ions, the popularization and application of the flow battery are facilitated, and meanwhile, the flow battery has the characteristics of long cycle life, simple structure and simple manufacturing process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a flow battery; the device comprises a 1-positive electrode end plate, a 2-negative electrode end plate, a 3-positive electrode, a 4-negative electrode, a 5-ion conducting membrane, a 6-circulating pump I, a 7-circulating pump II, an 8-positive electrolyte liquid storage tank and a 9-negative electrolyte liquid storage tank;
FIG. 2 shows the flow battery of Fe-Ti at 40mA/cm under the conditions of different Fe ion and Ti ion concentrations in example 1, example 2 and example 3 2 Is a performance under current density conditions;
FIG. 3 shows the FeTi flow battery at 40mA/cm under the conditions of different supporting electrolyte concentrations in example 4, example 5 and example 6 2 Under the current density condition of (2)Performance of (2);
FIG. 4 shows the flow batteries of example 7, example 8 and example 9 at 40mA/cm under different operating temperatures 2 Is a performance under current density conditions;
FIG. 5 is a graph of the example 10, example 11, and example 12 FeTi flow battery at 40mA/cm 2 Is a performance under current density conditions;
FIG. 6 is a graph of example 11 FeTi flow battery at 40mA/cm 2 Cyclic performance under current density conditions;
FIG. 7 is a graph of example 12 FeTi flow battery at 40mA/cm 2 Is a cyclic performance under current density conditions.
Detailed Description
The technical solution of the present invention will be further described with reference to the accompanying drawings and specific examples, without limiting the scope of the present invention.
A ferrotitanium flow battery with a structure shown in figure 1 comprises a battery module, an anode electrolyte liquid storage tank 8, a cathode electrolyte liquid storage tank 9, a circulating pump I6, a circulating pump II 7 and a circulating pipeline, wherein the battery module is formed by connecting one or more than two single batteries in series, each single battery comprises an electrode end plate (comprising an anode end plate 1 and a cathode end plate 2), a bipolar plate, an electrode (comprising an anode electrode 3 and a cathode electrode 4), an ion conducting membrane 5 and an electrode frame, the anode electrolyte liquid storage tank 8 is communicated with the anode electrode 3 of the battery module through the anode circulating pipeline, the cathode electrolyte liquid storage tank 9 is communicated with the cathode electrode 4 of the battery module through the cathode circulating pipeline, and the cathode redox couple of the battery is Ti 3+ /Ti 4+ The positive electrode redox couple is Fe 2+ /Fe 3+ The supporting electrolyte is an inorganic acid or an organic acid, and comprises one or a mixture of more of sulfuric acid, phosphoric acid, chloric acid, hydrochloric acid and methane sulfonic acid.
During charging, positive electrolyte and negative electrolyte are respectively conveyed to positive electrode and negative electrode from positive electrolyte liquid storage tank 8 and negative electrolyte liquid storage tank 9 respectively through circulating pump I6 and circulating pump II 7, ti 4+ Reduction of ions to Ti at the negative electrode 3+ Ion, fe 2 + Oxidation of ions to Fe at the positive electrode 3+ The method comprises the steps of carrying out a first treatment on the surface of the During discharge，Ti 3+ Oxidation of ions to Ti at the negative electrode 4+ Ions are returned to the negative electrolyte reservoir 9 via the circulation pump ii 7; fe (Fe) 3+ The ions are reduced to Fe at the positive electrode 2+ The ions are returned to the positive electrolyte reservoir 8 via the circulation pump i 6.
The positive and negative electrolyte is an acid solution containing iron ions and titanium ions, the proportion of the iron ions to the titanium ions is not limited, and the concentration of the iron ions is 0.1-5 mol & dm -3 The concentration of titanium ions is 0.1 to 5mol dm -3 The concentration of the acid is 0.1 to 6mol dm -3 。
The working temperature of the battery is-20-80 ℃.
The positive electrode 3 and the negative electrode 4 of the battery are made of metal or carbon materials with plate-shaped structures or porous structures, and the carbon materials comprise carbon cloth, carbon paper and carbon felt.
The ion-conducting membrane 5 is an ion-exchange membrane or a porous membrane.
Example 1
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 0.5mol/L is prepared 4 And 0.5mol/L TiOSO 4 H of 2.5mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
Example 2
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute and water isThe solvent, sulfuric acid as supporting electrolyte, is prepared to obtain FeSO with the composition of 1.0mol/L 4 And 1.0mol/L TiOSO 4 H of 2.5mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
Example 3
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1.5mol/L is prepared 4 And 1.5mol/L TiOSO 4 H of 2.5mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
The battery performance of examples 1-3 is shown in fig. 2, with the increase of the concentration of Fe/Ti in the electrolyte, the change of the coulomb efficiency of the battery is small, the voltage efficiency and the energy efficiency are increased and then decreased, because the increase of the ion concentration reduces the concentration polarization of the battery on the one hand, and improves the battery performance; on the other hand, the viscosity of the electrolyte is increased, the flow rate of the electrolyte is reduced under the action of the same lift circulating pump, the updating of the electrolyte near the electrode is hindered, the concentration polarization of the battery is enhanced, the dual functions of the electrolyte and the electrolyte reach the optimal balance in the embodiment 2, and the energy efficiency of the single battery test reaches the maximum of 83.5%.
Example 4
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 1mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
Example 5
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 3mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
Example 6
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 5mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
The battery performance of examples 4-6 is shown in fig. 3, with the increase of sulfuric acid concentration in the electrolyte, the change of coulombic efficiency of the battery is small, and the voltage efficiency and energy efficiency are increased and then decreased, because the increase of sulfuric acid concentration reduces the ohmic polarization of the battery and improves the battery performance; on the other hand, the viscosity of the electrolyte was increased, the concentration polarization of the cell was increased, and the dual effect of the two was optimally balanced in example 5, and the cell test energy efficiency was maximized at 84.1%.
Example 7
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 3mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at-10deg.C under constant temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
Example 8
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 3mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at 35deg.C under constant temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
Example 9
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 3mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
the charge and discharge test is carried out under the constant temperature environment of 70 ℃, 50mL of electrolyte is respectively used for the anode and the cathode, the flow rate is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V.
The battery performance of examples 7-9 is shown in fig. 4, where the battery coulombic efficiency gradually decreased and the voltage efficiency and energy efficiency increased as the cell test environment temperature increased. The temperature rise increases the diffusion coefficient of ions in the electrolyte, so that the phenomenon of cation cross interpenetrating is more serious; on the other hand, the high temperature can improve the electrochemical activity of iron ions and titanium ions, so that the electrochemical polarization of the battery is reduced, and the voltage efficiency is improved. Example 9 cell test energy efficiency reached a maximum of 85.5%.
Example 10
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, methanesulfonic acid is supporting electrolyte, feSO with the composition of 3mol/L is prepared 4 And 3mol/L TiOSO 4 And 1mol/L of methane sulfonic acid, as an electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V. Real worldAs shown in fig. 5, the battery performance of example 10 shows that the coulombic efficiency of the battery was 99%, the voltage efficiency was 80%, and the energy efficiency was 79.2% as shown in fig. 5.
Example 11
1. Electrolyte preparation:
by FeCl 2 And Ti (SO) 4 ) 2 Is solute, water is solvent, hydrochloric acid and sulfuric acid are supporting electrolyte, feCl with the composition of 5mol/L is prepared 2 And 5mol/L of Ti (SO) 4 ) 2 1mol/L HCl and 2mol/L H 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive membrane 5 (Nafion 211), negative electrode 4 (6X 8 cm) 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V. The battery performance of example 11 is shown in fig. 5, and as can be seen from fig. 5, the coulombic efficiency of the battery is 99%, the voltage efficiency is 76%, and the energy efficiency can reach 75.2%. The cycle life test was performed on the single cells, the cycle performance is as shown in fig. 6, and the efficiency was kept stable in 10000 cycles.
Example 12
1. Electrolyte preparation:
in FeSO 4 And TiOSO 4 Is solute, water is solvent, sulfuric acid is supporting electrolyte, feSO with the composition of 1mol/L is prepared 4 And 1mol/L TiOSO 4 H of 3mol/L 2 SO 4 As the electrolyte.
2. And (3) battery assembly:
the single cells are sequentially arranged according to a positive electrode end plate 1 and a positive electrode bipolar plate (7.5X9.5 cm) 2 ) Positive electrode 3 (6X 8 cm) 2 ) Ion conductive film 5 (SPEEK), negative electrode 4(6×8cm 2 ) Negative bipolar plate (7.5X19.5 cm) 2 ) The negative electrode terminal plate 2 is assembled.
3. And (3) battery testing:
performing charge and discharge test at room temperature, wherein the flow rate of electrolyte is 50mL/min, and the charge and discharge current density is 40mA/cm 2 The operating voltage is 0.3V to 0.9V. The battery performance of example 11 is shown in fig. 5, and as can be seen from fig. 5, the coulombic efficiency of the battery is 99%, the voltage efficiency is 86%, and the energy efficiency can reach 85.1%. The cycle life test was performed on the single cells, the cycle performance is as shown in fig. 7, and the efficiency was kept stable for 10000 cycles.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (6)

1. The utility model provides an iron titanium flow battery, the battery comprises battery module, positive pole electrolyte liquid storage pot, negative pole electrolyte liquid storage pot, circulating pump I, circulating pump II, circulation pipeline, the battery module is established ties by one or more single cell and is formed, the single cell contains electrode end plate, bipolar plate, electrode, ion conducting membrane, electrode frame, positive pole electrolyte liquid storage pot is linked together with battery module's positive pole through positive pole circulation pipeline, and negative pole electrolyte liquid storage pot is linked together with battery module's negative pole through negative pole circulation pipeline, its characterized in that, battery's negative pole redox couple is Ti 3+ /Ti 4+ The positive electrode redox couple is Fe 2+ /Fe 3+ The supporting electrolyte is sulfuric acid; the positive electrolyte is FeSO 4 The negative electrode electrolyte is TiOSO 4 。
2. According to claim 1The ferrotitanium flow battery is characterized in that during charging, positive electrolyte and negative electrolyte are respectively conveyed to a positive electrode and a negative electrode from a positive electrolyte liquid storage tank and a negative electrolyte liquid storage tank through a circulating pump, and Ti is added into the ferrotitanium flow battery 4+ Reduction of ions to Ti at the negative electrode 3+ Ion, fe 2+ Oxidation of ions to Fe at the positive electrode 3+ The method comprises the steps of carrying out a first treatment on the surface of the Upon discharge, ti 3+ Oxidation of ions to Ti at the negative electrode 4 + The ions are returned to the negative electrode electrolyte liquid storage tank through a circulating pump; fe (Fe) 3+ The ions are reduced to Fe at the positive electrode 2+ The ions are pumped back to the positive electrolyte reservoir via a circulation pump.
3. The iron-titanium flow battery of claim 1, wherein the Fe 2+ The concentration is 0.1 to 5mol dm -3 ，Ti 4+ The concentration is 0.1 to 5mol dm -3 Sulfuric acid concentration of 0.1-6mol.dm -3 。
4. The iron-titanium flow battery of claim 1, wherein the operating temperature of the battery is between-20 ℃ and 80 ℃.
5. The iron-titanium flow battery of claim 1, wherein the positive electrode and the negative electrode of the battery are made of metal or carbon materials with plate-shaped structures or porous structures, and the carbon materials comprise carbon cloth, carbon paper and carbon felt.
6. The iron-titanium flow battery of claim 1, wherein the ion conducting membrane is an ion exchange membrane.
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